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      Molecularly soldered covalent organic frameworks for ultrafast precision sieving

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          Abstract

          COF membrane was synthesized using a molecularly soldered strategy toward precise-sieving angstrom-sized contaminants.

          Abstract

          The weak interlamellar interaction of covalent organic framework (COF) nanocrystals inhibit the construction of highly efficient ion/molecular sieving membranes owing to the inferior contaminant selectivity induced by defects in stacked COF membranes and stability issues. Here, a facile in situ molecularly soldered strategy was developed to fabricate defect-free ultrathin COF membranes with precise sieving abilities using the typical chemical environment for COF condensation polymerization and dopamine self-polymerization. The experimental data and density functional theory simulations proved that the reactive oxygen species generated during dopamine polymerization catalyze the nucleophilic reactions of the COF, thus facilitating the counter-diffusion growth of thin COF layers. Notably, dopamine can eliminate the defects in the stacked COF by soldering the COF crystals, fortifying the mechanical properties of the ultrathin COF membranes. The COF membranes exhibited ultrafast precision sieving for molecular separation and ion removal in both aqueous and organic solvents, which surpasses that of state-of-the-art membranes.

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          Generalized Gradient Approximation Made Simple

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            A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu.

            The method of dispersion correction as an add-on to standard Kohn-Sham density functional theory (DFT-D) has been refined regarding higher accuracy, broader range of applicability, and less empiricism. The main new ingredients are atom-pairwise specific dispersion coefficients and cutoff radii that are both computed from first principles. The coefficients for new eighth-order dispersion terms are computed using established recursion relations. System (geometry) dependent information is used for the first time in a DFT-D type approach by employing the new concept of fractional coordination numbers (CN). They are used to interpolate between dispersion coefficients of atoms in different chemical environments. The method only requires adjustment of two global parameters for each density functional, is asymptotically exact for a gas of weakly interacting neutral atoms, and easily allows the computation of atomic forces. Three-body nonadditivity terms are considered. The method has been assessed on standard benchmark sets for inter- and intramolecular noncovalent interactions with a particular emphasis on a consistent description of light and heavy element systems. The mean absolute deviations for the S22 benchmark set of noncovalent interactions for 11 standard density functionals decrease by 15%-40% compared to the previous (already accurate) DFT-D version. Spectacular improvements are found for a tripeptide-folding model and all tested metallic systems. The rectification of the long-range behavior and the use of more accurate C(6) coefficients also lead to a much better description of large (infinite) systems as shown for graphene sheets and the adsorption of benzene on an Ag(111) surface. For graphene it is found that the inclusion of three-body terms substantially (by about 10%) weakens the interlayer binding. We propose the revised DFT-D method as a general tool for the computation of the dispersion energy in molecules and solids of any kind with DFT and related (low-cost) electronic structure methods for large systems.
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              Mussel-inspired surface chemistry for multifunctional coatings.

              We report a method to form multifunctional polymer coatings through simple dip-coating of objects in an aqueous solution of dopamine. Inspired by the composition of adhesive proteins in mussels, we used dopamine self-polymerization to form thin, surface-adherent polydopamine films onto a wide range of inorganic and organic materials, including noble metals, oxides, polymers, semiconductors, and ceramics. Secondary reactions can be used to create a variety of ad-layers, including self-assembled monolayers through deposition of long-chain molecular building blocks, metal films by electroless metallization, and bioinert and bioactive surfaces via grafting of macromolecules.
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                Author and article information

                Journal
                Sci Adv
                Sci Adv
                SciAdv
                advances
                Science Advances
                American Association for the Advancement of Science
                2375-2548
                March 2021
                24 March 2021
                : 7
                : 13
                : eabe8706
                Affiliations
                [1 ]MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, State Key Laboratory of Urban Water Resource and Environment, and School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001, China.
                [2 ]School of Environment, Harbin Institute of Technology, Harbin 150009, China.
                [3 ]Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139, USA.
                [4 ]College of Environment and Resources, Fuzhou University, No. 2 Xueyuan Road, Fujian 350116, China.
                [5 ]School of Engineering, The University of Edinburgh, King’s Buildings, Mayfield Road, Edinburgh EH9 3JL, UK.
                Author notes
                [* ]Corresponding author. Email: shaolu@ 123456hit.edu.cn
                Author information
                http://orcid.org/0000-0001-7189-4214
                http://orcid.org/0000-0001-8943-569X
                http://orcid.org/0000-0002-4161-3861
                Article
                abe8706
                10.1126/sciadv.abe8706
                7990329
                33762342
                9a840ab7-864f-428e-98b0-f8b0ed2e9ffa
                Copyright © 2021 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).

                This is an open-access article distributed under the terms of the Creative Commons Attribution-NonCommercial license, which permits use, distribution, and reproduction in any medium, so long as the resultant use is not for commercial advantage and provided the original work is properly cited.

                History
                : 21 September 2020
                : 04 February 2021
                Funding
                Funded by: doi http://dx.doi.org/10.13039/501100001809, National Natural Science Foundation of China;
                Award ID: 21878062
                Funded by: State Key Laboratory of Urban Water Resource and Environment (Harbin Institute of Technology);
                Award ID: 2020DX02
                Funded by: Natural Science Foundation of Heilongjiang Province for Distinguished Young Scholars;
                Award ID: JQ2020B001
                Categories
                Research Article
                Research Articles
                SciAdv r-articles
                Materials Science
                Applied Sciences and Engineering
                Materials Science
                Custom metadata
                Anne Suarez

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